Process for the preparation of botadiene from N-butene

ABSTRACT

Catalysts containing molybdenum, bismuth, iron and nickel, cobalt, magnesium, zinc, cadmium, manganese calcium or mixture thereof and an alkali metal or T1 are promoted by an element selected from antimony and tin to give highly desirable catalysts for the oxidative dehydrogenation of olefins of 4 to about 10 carbon atoms.

United States Patent 1191 [111 3,91 1,039 Grasselli et al. 51 Oct. 7,1975 PROCESS FOR THE PREPARATION OF 3.642,930 2/1972 Grasselli et a1260/680 E BUTADIENE FROM N'BUTENE 8???) 37133? lif f f""" 32352385 ratse a [75] In n Robert Grasselli, Chagrin Falls; 3,825,502 7 1974 Takenakaet al. 252/456 Harley F. l-lardman, Lyndhurst, both of Ohio PrzmaryExaminer-Paul M. Coughlan, Jr. Assignee: The Standard on p y Attorney,Agent, or Firm-Herbert D. Knudsen Cleveland, Ohio [22] Filed: Jan. 23,1974 [57] ABSTRACT [21] Appl. No.: 435,841

Catalysts containing molybdenum, bismuth, iron and nickel, cobalt,magnesium, zinc, cadmium, manganese g 260/680 calcium or mixture thereofand an alkali metal or T1 [58 Fl? id 260/280 E are promoted y an elementSelected from antimony 1 le 0 care and tin to give highly desirablecatalysts for the oxida- References Cited Live dehydrogenation ofolefins of 4 to about 10 caron atoms. UNITED STATES PATENTS 3,414,63112/1968 Grasselli et al 260/680 E 3 Claims, No Drawings PROCESS FOR THEPREPARATION OF BOTADIENE FROM N-BUTENE BACKGROUND OF THE INVENTION Theoxidative dehydrogenation of olefins is known, see for example U.S. Pat.Nos. 3,414,631 and 3,642,930. The process of the present invention isconducted within the parameters of the art, but uses a differentcatalyst.

SUMMARY OF THE INVENTION It has been discovered in the process for theoxidative dehydrogenation of 1 an olefinic hydrocarbon of 4 to aboutcarbon atoms comprising contacting-a mixture of the olefin and molecularoxygen with a catalyst at a temperature of about 200 to about 600C, theimprovement comprising using as the catalyst a catalyst wherein theatomic ratios of the elements are described by the empirical formula A CD Fe Bi; M0 O wherein A is tin, antimony or mixture thereof;

C is an alkali metal, T1 or mixture thereof; and D is nickel, cobalt,magnesium, zinc, cadmium, manganese, calcium or mixture thereof; andwherein a and c are 0.01 to about 4;

d is 0.1 to about e and f are 0.1 to 12; and

x is the number of oxygens required by the valence states of the otherelements present. The process of the invention gives highly desirableyields of the diolefin product, long catalyst life is realized and largevolumes of product can be produced in a given period of time.

The present invention is the use of a different catalyst in the knownoxidative dehydrogenation of olefins. The central aspect of thisinvention is the catalyst.

The catalyst is suitably any catalyst containing the combination ofelements delimited by the formula above. Preferred are catalysts thatcontain nickel, cobalt, magnesium or mixture thereof and those catalyststhat contain potassium.

The catalysts of the invention are conveniently prepared by any of themethods associated with the similar oxidation catalysts in the art.Among the method of combining the elements of the catalyst are thecoprecipitation of soluble salts from a solution and the mixing of saltsor oxides of the various compounds. After the elements of the catalystare combined, the preparation of the catalyst is completed bycalcination of the catalyst at an elevated temperature. Temperaturesbetween about 200 and about 600C. are most suitable.

Specific preparations of catalysts of the invention are shown in thespecific embodiments. These preparations give preferred catalysts of theinvention.

The catalysts of the invention may be used as pure catalytic material orthey may be used in a supported form. Suitable support materials includesilica, alumina, titania, zirconia, boron phosphate and the like. Theuse of catalysts supported on silica is preferred.

The oxidative dehydrogenation reaction of the invention is known. Theinvention is operated within the parameters of the art processes eventhough a different catalyst is employed.

Broadly, the reaction of the invention reacts an olefin of 4-10 carbonatoms with molecular oxygen, normally added as air, in the presence of acatalyst. The ratio of molecular oxygen is normally about 0.2 to about 6moles of oxygen per mole of olefin, but ratios outside of this range arealso conveniently used. The reactants could be diluted with a diluentsuch as steam.

Preferred reactants in the present invention are the n-butenes which areconverted to butadiene by the process of the invention. Also preferredis the reaction of isoamylene to obtain isoprene.

The reaction is normally conducted at temperatures between about 200 andabout 600C., with temperatures of about 300 to about 500C. beingpreferred. The reactants can be passed over the catalyst at an apparentcontact time as low as a fraction of a second to 20 seconds or more. Thereaction can be conducted in a fluid-bed or fixed-bed reactor atatmospheric, superatmospheric or subatmospheric pressure. Using thesetechniques, the reaction of the present invention gives highly desirableyields of diolefins from the corresponding olefin.

EXAMPLES 1-12 Oxidative Dehydrogenation With Various Catalysts of theInvention Various catalysts of the invention were prepared as follows:

EXAMPLES 1-5 Sb K Ni Co ,Fe BiMo 0, and 20% SiO An aqueous slurrycontaining 63.54 g. (NI-l Mo O -4 O, 52.06 g. of 40 percent Nalco silicasol and 2.19 g. of Sb O was prepared. Separately, a solution containing36.36 g. of Fe(NO 91-1 0, 14.55 g. Bi(NO 51-1 0, 39.29 g. Co(NO 611 0,21.81 g. of Ni(NO 6H O and 3.03 g. of a 10% KNO solution was prepared.The solution was added to the slurry and the resulting mixture wasevaporated to a paste material. The paste was dried overnight in an ovenat 1 10C. The dry material obtained was heated at 290C. for 3 hours,425C. for 3 hours and 550C. for 16 hours.

EXAMPLES 6-8 80% Sn K Ni Co Fe BiMo O and 20% SiO The catalyst wasprepared in the same manner as above except that 2.26 g. of SnO wasadded instead of the antimony oxide.

The catalyst was prepared in exactly the same manner as above exceptthat potassium nitrate was doubled.

EXAMPLES 10 and 11 80% Sb Cs Ni Co Fe BiM0 0 and 20% SiO The catalystwas prepared in the same manner as above except that 2.93 g. of a 10percent solution of CsNO was added instead of the potassium nitrate.

EXAMPLE 12 80% Sb Tl Ni co Fe BiMo 0, and 20% SiO The catalyst wasprepared in the same manner as Examples l except that 1.60 g. of TI N0was added instead of potassium.

A reactor was constructed of a stainless steel tube having a 2.5 cc.Zone for catalyst. A 20 by 30 mesh fraction of the catalyst was chargedto the reaction zone, the reactor was brought to reaction conditionsunder a flow of air. The critical reaction parameters are given in thefollowing Table. The catalyst is designated in the Table as A,,Ni Co FeBiMo 0,. It is understood that all catalysts contained 20 percentsilica. Butene-2 was used as a mixture of 57.5 percent trans and 42.5percent cis butent-2.

The results of these experiments are stated in the following terms:

% conversion selectivity EXAMPLE l4 Catalyst Containing Magnesium In thesame manner as shown above, a catalyst containing 80% Sb K Mg Ni Co FeBiMo o and 20% SiO was prepared and tested according to the conditionsof Example 13. The conversion was 85.0 percent, the selectivity 94percent and the single pass yield to butadiene was 79.9 percent.

In the same manner, other catalysts of the invention can be prepared andused to produce butadiene from butene'2 or butene-l.

With various catalysts of the invention, it has been found that thetreatment of the catalyst with a flow containing ammonia prior to thereaction at reaction temperature enhances the activity of the catalystsin the oxidative dehydrogenation. This treatment with ammonia can takeplace in the presence of air and/or a hydrocarbon.

We claim:

1. In the process for the oxidative dehydrogenation of n-butene tobutadiene comprising contacting a mixture of the n-butene and molecularoxygen with a catalyst at a temperature of about 200 to about 600C, theimprovement comprising using as the catalyst a catalyst wherein theatomic ra- Table Oxydehydrogenation of Butene Using t,,Ni Co Fe,,BiMo 0Catalyst Butene-X, Temp. C.T. Conver- Selec- Single Pass Example A,,= X=Air Steam C. Sec. sion tivity Yield 1 Sb,, .,l 1 1 1 0 350 1.0 100 9090.3 2 sb,, .,K,, 2 1 1 0 350 1.0 96.5 92 88.9 3 $6, 16,, 2 31 0 350 1.099.9 90 90.1 4 Sb (L, 2 31 0 340 1.0 96.3 93 89.7 5 $6 K 2 8O 0 350 0.694.9 88 83.6 6 si-|,, .,1 1 11 4 350 1.0 98.7 97 95.7 7 sn,, ,1 1 31 0400 1.0 96.4 90 86.2 8 sn K 2 31 0 350 1.0 93.9 94 88.2 9 Sb,, K., 2 310 350 1.0 96.9 97 93.8 10 Sbu C u 1,5 2 31 0 350 1.0 75.6 92 69.3 11 231 0 375 1.0 83.1 86 71.6 12 Sb Tl 2 3 l 0 350 l .0 81.6 98 80.0

tios are described by the empirical formula Sb C D Fe Bi, M0 0,

wherein C is an alkali metal, Tl or mixture thereof; and D is nickel;cobalt, magnesium, zinc, cadmium, manganese, calcium or mixture thereof;EXAMPLE 13 and Wherem Catalyst Containing More Silica a and c are 0.01to about 4; d is 0.1 to about 20; e andf are 0.1 to 12; and x is thenumber of oxygens required by the valence states of the other elementspresent. 2. The process of claim 1 wherein D is nickel, cobalt,magnesium or mixture thereof.

3. The process of claim 1 wherein C is potassium.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,911 ,039 DATED October 7, 1975 |NVENTOR(S) Robert K. Grasselli et altt'is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below: 0

Column 1: Line 49, "method" should be --methods-- Column 2: Line 26,title "Specific Embodiments" should be inserted Column 2: Line 38, "4 0"should be "41-1 0" Column 2: Line 41, Bi(NO should be--Bi (N0 Column 4;Line 44, "Sb should read Sb o Signed and Scaled this Twenty-eighth Dayof December 1976 sen AIIESI.

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oj'Patentsand Trademarks

1. IN THE PROCESS FOR THE OXIDATIVE DEHYDROGENATION OF NBUTENE TOBUTADIENE COMPRISING CONTACTING A MIXTURE OF THE N-BUTENE AND MOLECULAROXYGEN WITH A CATALYST AT A TEMPERATURE OF ABOUT 200* TO ABOUT 600*C.,THE IMPROVEMENT COMPRISING USING AS THHE CATALYST A CATALYST WHEREIN THEATOMIC RATIOS ARE DESCRIBED BY THE EMPIRICAL FORMULA
 2. The process ofclaim 1 wherein D is nickel, cobalt, magnesium or mixture thereof. 3.The process of claim 1 wherein C is potassium.